CN104040347A - A sensor composition for acetone detection in breath - Google Patents
A sensor composition for acetone detection in breath Download PDFInfo
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- CN104040347A CN104040347A CN201380004960.9A CN201380004960A CN104040347A CN 104040347 A CN104040347 A CN 104040347A CN 201380004960 A CN201380004960 A CN 201380004960A CN 104040347 A CN104040347 A CN 104040347A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/483—Physical analysis of biological material
- G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
- A61B5/082—Evaluation by breath analysis, e.g. determination of the chemical composition of exhaled breath
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
- A61B5/083—Measuring rate of metabolism by using breath test, e.g. measuring rate of oxygen consumption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/64—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving ketones
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
- A61B5/14532—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue for measuring glucose, e.g. by tissue impedance measurement
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/483—Physical analysis of biological material
- G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
- G01N2033/4975—Physical analysis of biological material of gaseous biological material, e.g. breath other than oxygen, carbon dioxide or alcohol, e.g. organic vapours
Abstract
The present invention provides a composition for acetone detection and a process of preparation thereof. The composition comprises gamma-ferric oxide (gamma-Fe2O3), antimony (Sb) salt, and platinum (Pt). The sensor fabricated using the said composition is selective to low concentration of breath acetone, the biomarker of diabetes, in presence of high amount of moisture normally present in breath. Such semiconductor sensors for diabetes monitoring are inexpensive, rugged, patient-friendly and on the top, non-invasive.
Description
Technical field
The present invention relates to diagnostic method and compositions field.More specifically, it relates to the composition detecting for acetone.More specifically, it relates to the composition and method of making the same that the acetone in the breathing that can be used for diabetes diagnosis detects.Composition of the present invention comprises gamma-iron oxide (γ-Fe
2o
3), antimony (Sb) salt and platinum (Pt).
Background technology
Threat extend over the entire globe and diabetic's ratio of diabetes constantly increase.India will become the maximum country of diabetes very soon.Yet the early detection of diabetes can reduce the potential danger of this fatal disease.Blood sugar monitoring (fasting plasma glucose and oral glucose tolerance test) is the reliable method that the diabetes of elapsed time check detect.Yet the method is expensive, and first and foremost, be to there is a kind of invasive method.In order to address this problem, after deliberation different without wound and minimal invasive techniques as the optical activity of IR spectrum, polarized light, radiowave impedance, tear analysis, extraction from the analysis of the fluid of skin and from one bleeds the biology sensor of monitoring diabetes.Up to now, also do not have commercially available for monitor diabetes without wound family expenses small tool.
Up to now, attempted manyly different without wound and minimal invasive techniques (as mentioned above), monitoring diabetes [1,2].In addition, for a long time, the known increase of the acetone concentration in human body respiration in diabetic.Provide, the acetone concentration <0.9ppm in breathing can be used as the normal value of healthy individual, and concentration >1.7ppm shows diabetes [1,2].Between the acetone concentration of breathing and blood sugar level, also there is good correlativity [3].At high-precision instrument, carried out the research [4,5] of great majority about acetone measurement in breathing on as GC-MS, SFFT-MS and cavity ring-down spectroscopy (cavity ring down spectroscopy).Additive method is the measurement based on pyruvic acid (US7118919B2, USRE38575E and WO1999/56790A2), ionic mobility spectrophotometer (US6794645B2) of C-13 mark, the microplasma (US7417730B2, US2004/137637A1) [6,7] of being combined with spectrometer etc.In addition, recently after deliberation metal-oxide semiconductor (MOS) (as SnO
2, WO
3, ZnO and TiO
2) for the detection (WO2011/068976A1) [7-20] of low concentration acetone, because semiconductor transducer low price, sturdy and durable and be convenient for carrying.For example, the TiO of Ag modified by nano particles
2sensor has the acetone steam detectability [8] of 10ppm and the acetone detectability of ZnO nano-wire and dumb-bell-shaped ZnO microcrystal is low to moderate respectively 5ppm and 1ppm[14,15].Reported in the early time and under the gentle working temperature of 150 ℃, used not doping or doped gamma-Fe
2o
3the acetone sensitivity [1,9] of the sub-ppm of sensor.The SiO of 10mol%
2ε-the WO of doping
3composition shows the enough sensitivity [20] in low concentration (100ppb to the 900ppb) acetone steam under the working temperature of 400 ℃.
Up to now, the shortcoming of the metal oxide semiconductor sensor of research is:
I) for manufacturing installation, high in the insufficient sensitivity of low ppm or sub-ppm range detection acetone concentration.
Ii) sensor of prior art report to moisture-sensitive and therefore under high-moisture amount exists (being conventionally present in breathing) acetone is not had to selectivity.
Consider the shortcoming of prior art sensor, the inventor has developed the composition of these shortcomings that overcome prior art sensor.The sensor of the composition manufacture of request for utilization protection shows appreciable sensitivity and the high selectivity under about 1ppm acetone concentration, and simultaneously insensitive to the high-moisture amount being present in breathing.
Goal of the invention
Fundamental purpose of the present invention is to provide the composition and method of making the same detecting for acetone.
Another object of the present invention is to provide the improved composition and method of making the same of the low concentration acetone detection (about 1ppm) for breathing.
Another object of the present invention is to provide the composition and method of making the same based on metal-oxide semiconductor (MOS), and described composition detects the acetone in breathing for low concentration selectivity under the existence of the high-moisture amount in breathing.
Another object of the present invention is to provide the composition and method of making the same based on metal-oxide semiconductor (MOS) for diabetes diagnosis, and described composition is for the detection of low concentration acetone in the breathing under the existence of the high-moisture amount in breathing.
Summary of the invention
The invention provides the composition and method of making the same detecting for breathing acetone.The described composition detecting for acetone comprises gamma-iron oxide (γ-Fe
2o
3), antimony (Sb) salt and platinum (Pt).Described composition shows the appreciable sensitivity under about 1ppm acetone concentration and is insensitive for the high-moisture amount being conventionally present in breathing.The invention provides the composition detecting for the breathing acetone diabetic.
The explanation of accompanying drawing and table
Fig. 1 is illustrated under the working temperature of 300 ℃, γ-Fe of embodiment 1
2o
3based sensor is to the 1ppm acetone steam in air (RH approximately 45%) and the response of saturation moisture.
Fig. 2 is illustrated under the working temperature of 300 ℃, γ-Fe of embodiment 1
2o
3the responsiveness (percent response) of based sensor to the acetone steam of variable concentrations in air (RH approximately 45%).
Table 1 data are illustrated under the working temperature of 300 ℃, γ-Fe
2o
3based sensor is for the 1ppm acetone steam in air (RH approximately 45%) and the gas-sensitive property of the 1ppm acetone steam in saturation moisture.
Embodiment
Therefore, the invention provides the composition detecting for acetone, it comprises gamma-iron oxide (γ-Fe
2o
3), antimony (Sb) salt and platinum (Pt).
One embodiment of the invention provide the composition detecting for acetone, and it comprises gamma-iron oxide, antimonic salt and platinum.
In another aspect of the present invention, antimonic salt be with oxide, carbonate, nitrate or arbitrarily the form of other salt add.
In another aspect of the present invention, platinum be with metallic forms, chloride, nitrate or arbitrarily the form of other salt add.
In another aspect of the present invention, the concentration range of gamma-iron oxide is 87.5wt% to 95.7wt%.
In another aspect of the present invention, the concentration range of antimonic salt is 2.9wt% to 9.9wt%.
In another aspect of the present invention, the concentration range of platinum is 0.5wt% to 2.6wt%.
In another embodiment of the invention, by the phonochemistry method comprising the following steps, prepare composition:
(a) by adding water and hydrochloric acid, prepare Fe(NO3)39H2O (III) salt [Fe (NO
3)
39H
2o], aqueous solution separately of antimonic salt and platinum salt and at 100 ℃ of these solution of heating;
(b) aqueous solution that for example, will form in step (a) with required ratio (described herein) is to form mixed solution;
(c) by the mixed solution sonication forming in step (b) and add hydrazine to generate sediment during sonication;
(d) sediment forming in step (c) is centrifugal, washing and dry to obtain gamma-iron oxide based powders.
In another aspect of the present invention, antimonic salt be with oxide, carbonate, nitrate or arbitrarily the form of other salt add.
In another aspect of the present invention, platinum be with metallic forms, chloride, nitrate or arbitrarily the form of other salt add.
In another embodiment of the invention, the method for manufacturing sensor with described composition comprises the following steps:
A) gamma-iron oxide based powders is mixed to form slurry with isopropyl alcohol;
B) thus get substrate and it heated gold electrode and platinum filament are attached to substrate at the temperature of 1000 ℃;
C) get as slurry prepared in step (a) and drip on the substrate that is coated in rotation and drip to manufacture the substrate being coated with;
D) substrate of described painting is hardened at the temperature within the scope of 200 ℃ to 450 ℃;
E) cantar alloy (kanthal) heater coil is inserted into described dripping in the substrate being coated with; And
F) by wire-bonded/soldering, the substrate that is coated with sensor is fixed on transistor outline (TO) type packaging body to form sensor.
In another aspect of the present invention, described sensor manufactures thick film on substrate or form and/or the block form of film.
In another aspect of the present invention, substrate is selected from aluminium oxide or insulating material and is the form of pipe, planar structure or the microheater based on MEMS (micro electro mechanical system) (MEMS).
In another embodiment of the invention, use the sensor of described composition under the existence of high-moisture amount, to detect the acetone concentration of 1ppm and sub-ppm.
In another embodiment of the invention, described composition is used for to diagnosing diabetes and the relevant disease with abnormal acetone concentration.
Another embodiment of the present invention provides for sensor combinations thing of the breathing acetone detection of diabetes diagnosis and preparation method thereof, and described sensor combinations thing comprises about 87.5wt% to γ-Fe of about 95.7wt%
2o
3, about 2.9wt% is to the Sb of about 9.9wt%
2o
3with the platinum of about 0.5wt% to about 2.6wt%.
For the real world applications of the semiconductor transducer for diabetes diagnosis, it tackles acetone (the breathing biomarkers of the diabetes) sensitivity of about 1ppm concentration.In addition, the acetone of its reply in breathing have selectivity and primary be that high-moisture amount to being present in breathing is insensitive or responsive hardly.Last standard is to be difficult to realize, because semiconductor transducer is notoriously to moisture-sensitive.
The invention provides and meet above-mentioned standard and the particularly composition of very inaccessible last standard.According to Primary Study, by the inventor use the sensor of composition manufacture of the present invention show healthy individual on the feed before and feed after different breathings in acetone level.In addition the height that the sensor that, Primary Study illustrates the composition manufacture of the application of the invention can detect in diabetic is breathed acetone level.
Conventionally, Fe
2o
3be easy to as α-Fe
2o
3and obtain.Yet, need to adjust treatment step to obtain the Fe of " γ " form
2o
3.What is interesting is, conventional chemical precipitation route provides α-Fe
2o
3, and phonochemistry method is because cavitation provides nano level γ-Fe
2o
3, described cavitation produces local high moderate pressure.Thereby the particle for the manufacture of the composition of sensor should be easy to obtain improved sensitivity, response and release time by phonochemistry method in nanoscale scope.
In order to prepare sensor combinations thing, (about 87.5wt% is to γ-Fe of about 95.7wt%
2o
3, about 2.9wt% is to the Sb of about 9.9wt%
2o
3with the Pt of about 0.5wt% to about 2.6wt%), by adding hydrochloric acid (HCl), manufacture molysite (Fe (NO
3)
3.9H
2o), antimonic salt (SbCl
3), platinum salt (anhydrous PtCl
4) aqueous solution separately and heat this solution at 100 ℃.With required ratio, solution is mixed, by the solution sonication of mixing and during sonication, hydrazine is added in solution.Sediment is centrifugal and with distilled water washing, dry to obtain γ-Fe in baking oven
2o
3based powders.Yet, also can for example, by the method (solid-state, softening learning and gas phase process) of having reported in prior art, prepare γ-Fe
2o
3.
Composition of the present invention is for manufacturing thick film, film or block gas sensor according to technology known in the art.Sensor platform can be tubulose aluminium oxide or other dielectric substrate, plane oxidation aluminium or other dielectric substrate or MEMS base microheater/miniature hot plate.This paper describes a kind of exemplary techniques.
γ-Fe of about 0.0015g will be amounted to
2o
3based powders mixes to form slurry with the isopropyl alcohol of 1mL.With micropipettor, get the slurry of approximately 40 μ L, then drip (internal diameter of the length of about 4mm, the external diameter of 1.5mm and 1mm) on the alumina tube that is coated in rotation, on it, at each end, be placed with two gold electrodes and platinum filament.Before using paste, by stiffening system under high temperature (approximately 1000 ℃), gold electrode and platinum wire are attached to the end of pipe.At approximately 300 ℃, with the rate of heat addition of 50 ℃/h, fire the alumina tube 1 hour of coating.Then cantar alloy heater coil is placed on to Al
2o
3pipe is interior to produce optimum working temperature.By engage/soldering of line, the alumina tube that is coated with sensor is fixed on TO (transistor outline) transistor npn npn packaging body.Before sensitivity measure, by sensor 250 ℃ initial aging 72 hours to reach the stability of expectation.Use digital multimeter (Agilent U1252A) and constant voltage/current source (Keithley228A) in resistance, response number percent and recovery and the response time of the lower survey sensor of different temperature (200 ℃ to 350 ℃).Sensor to be measured be placed in the centre of quartz ampoule (2cm diameter and 10cm length) and through digital multimeter and the outside connecting sensor of constant voltage/current source to record sensor resistance.Under different working temperatures, sensor is exposed in the steam of steam, saturation moisture and the low concentration acetone in the surrounding environment of saturation moisture of airborne low concentration acetone.In exsiccator, by serial dilution, prepare low concentration acetone steam.The number percent of response, S (equaling sensitivity) is defined as,
Wherein, R
aairborne sensor resistance under working temperature, and R
git is the sensor resistance in target steam at the same temperature.
Non-obvious inventive step is to find out has selectivity and to being present in the insensitive composition of high-moisture amount in breathing to the low concentration acetone in breathing.Platinum is a kind of in noble metal catalyst, and it has improved the acetone sensitivity of sensor.Yet together with the sensitivity of acetone, platinum has also improved water sensitivity.The interpolation of sb oxide has significantly reduced water sensitivity and has not affected acetone sensitivity.The generation of this situation can be because of the following fact: conventionally, the oxyhydroxide of heavy metal (as iron) the performance water of sening as an envoy to ruptures and becomes the tendency of oxide or hydrous oxid, because O
2-the comparable OH of ion
-ion screens (screen) kation better.Yet, in a humid environment, some OH
-ion can be attached to Fe
3+on.Comparatively speaking, when antimony ion is present in ferriferous oxide, OH
-antimony ion should preferentially be attached on antimony ion, because can be expanded its coordination number to accept except its O of coordination
2-oH outside ion
-ion, and therefore, the combination of antimony has reduced γ-Fe
2o
3water sensitivity.
By work in practice of explanation the present invention, provided following examples, and these embodiment should not be construed as by any way and limit the scope of the invention.
Embodiment 1
In order to prepare the Sb that contains 5.7wt%
2o
3, the Pt of 1.4wt% and γ-Fe of 92.9wt%
2o
3composition, prepared following solution: a) 2.424g Fe (NO
3) 9H
2o (Merck, 99% purity) in 250mL distilled water, b) 6.25g NH
2nH
2h
2o (hydrazine) (Qualigens, 99% purity) in the distilled water of 250mL, c) the anhydrous PtCl of 0.0124g
4(Merck) in 20mL distilled water under the existence of 2mL concentrated hydrochloric acid in 100 ℃ of continuous stirring 1 hour, and d) 0.0046g SbCl
3(Sigma-Aldrich, 99% purity) in 20mL distilled water under the existence of 3mL concentrated hydrochloric acid in 100 ℃ of continuous stirring 1 hour.
In 500mL beaker, the aqueous solution of molysite, antimonic salt, platinum salt is adjusted to 300mL together and by the final volume of solution, then stirs 10 minutes.The length that solution in beaker is placed in ultrasonic device (processor for ultrasonic wave, Sonics, 1500 watts, model VCF1500) and probe (diameter 2cm) immersion solution is about 4cm.During sonication (sonication time 2 h), by 0.5M hydrazine (N
2h
4h
2o) the pH value that aqueous solution (as above preparation) thereby dropwise add obtains expectation is about 8 solution and completely precipitates.Make solution cooling and when reaction finishes, obtained the coloured sediment of muddy.After sonication completes, by solution centrifugal being isolated to the particle being obtained for 15 minutes with 10000rpm.By centrifugal by particle washing several in distilled water.Finally, muddy colored powder is dried to 16 hours in 100 ℃ in vacuum drying oven.
By as at the synthetic powder that provides of part before, manufactured sensor, and as before part is described has studied air-sensitive behavior.
In Fig. 1 of Figure of description and Fig. 2, describe the present invention.In the accompanying drawings, Fig. 1 is illustrated under the working temperature of 300 ℃, γ-Fe of embodiment 1
2o
3based sensor is to the 1ppm acetone steam of (RH approximately 45%) and the response of saturation moisture in air; Fig. 2 is illustrated under the working temperature of 300 ℃, γ-Fe of embodiment 1
2o
3the responsiveness of based sensor to the acetone steam of the variable concentrations of (RH approximately 45%) in air.
Table 1: data are illustrated under the working temperature of 300 ℃, γ-Fe
2o
3based sensor is to the 1ppm acetone steam in air (RH approximately 45%) and the gas-sensitive property of the 1ppm acetone steam in saturation moisture.
Embodiment 2
In order to prepare the Sb that contains 2.9wt%
2o
3, the Pt of 1.4wt% and γ-Fe of 95.7wt%
2o
3composition, prepared following solution: a) 2.424g Fe (NO
3) 9H
2o (Merck, 99% purity) in 250mL distilled water, b) 6.25g NH
2nH
2h
2o (Qualigens, 99% purity) in the distilled water of 250mL, c) the anhydrous PtCl of 0.0124g
4(Merck) in 20mL distilled water under the existence of 2mL concentrated hydrochloric acid in 100 ℃ of continuous stirring 1 hour, and d) 0.0023gSbCl
3(Sigma-Aldrich, 99% purity) in 20mL distilled water under the existence of 3mL concentrated hydrochloric acid in 100 ℃ of continuous stirring 1 hour.
In 500mL beaker, the aqueous solution of molysite, antimonic salt, platinum salt is adjusted to 300mL together and by the final volume of solution, then stirs 10 minutes.The length that solution in beaker is placed in ultrasonic device (processor for ultrasonic wave, Sonics, 1500 watts, model VCF1500) and probe (diameter 2cm) immersion solution is about 4cm.During sonication (sonication time 2 h), by 0.5M hydrazine (N
2h
4h
2o) to obtain the pH value of expectation be that approximately 8 solution precipitates completely for aqueous solution (as above preparation) thereby dropwise add.Make solution cooling and when reaction finishes, obtained the coloured sediment of muddy.After sonication completes, by solution centrifugal being isolated to the particle being obtained for 15 minutes with 10000rpm.By centrifugal by particle washing several in distilled water.Finally, muddy colored powder is dried to 16 hours in 100 ℃ in vacuum drying oven.
By as at the synthetic powder that provides of part before, manufactured sensor, and as before part is described has studied air-sensitive behavior.
Embodiment 3
In order to prepare the Sb that contains 9.9wt%
2o
3, the Pt of 2.6wt% and γ-Fe of 87.5wt%
2o
3composition, prepared following solution: a) 2.424g Fe (NO
3) 9H
2o (Merck, 99% purity) in 250mL distilled water, b) 6.25g NH
2nH
2h
2o (Qualigens, 99% purity) in the distilled water of 250mL, c) the anhydrous PtCl of 0.0248g
4(Merck) in 20mL distilled water under the existence of 2mL concentrated hydrochloric acid in 100 ℃ of continuous stirring 1 hour, and d) 0.0085g SbCl
3(Sigma-Aldrich, 99% purity) in 20mL distilled water under the existence of 3mL concentrated hydrochloric acid in 100 ℃ of continuous stirring 1 hour.
In 500mL beaker, the aqueous solution of molysite, antimonic salt, platinum salt is adjusted to 300mL together and by the final volume of solution, then stirs 10 minutes.The length that solution in beaker is placed in ultrasonic device (processor for ultrasonic wave, Sonics, 1500 watts, model VCF1500) and probe (diameter 2cm) immersion solution is about 4cm.During sonication (sonication time 2 h), by 0.5M hydrazine (N
2h
4h
2o) to obtain the pH value of expectation be that approximately 8 solution precipitates completely for aqueous solution (as above preparation) thereby dropwise add.Make solution cooling and when reaction finishes, obtained the coloured sediment of muddy.After sonication completes, by solution centrifugal being isolated to the particle being obtained for 15 minutes with 10000rpm.By centrifugal by particle washing several in distilled water.Finally, muddy colored powder is dried to 16 hours in 100 ℃ in vacuum drying oven.
By as at the synthetic powder that provides of part before, manufactured sensor, and as before part is described has studied air-sensitive behavior.
Advantage of the present invention:
I. described composition detects the acetone of the following concentration of 1ppm.
Ii. described composition detects the low concentration acetone in high moisture environments.
Iii. described composition optionally detects in breathing particularly and to breathe the acetone of higher moisture under existing, as found by research institute before.
Iv. described composition be for from human breathing, carry out diabetes diagnosis there is cost benefit, simple, sturdy and durable, patient is friendly and the potential material standed for of noninvasive sensor.
List of references:
The publication of quoting:
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1-xTi
xO
3?perovskite?system?prepared?by?amorphous?citrate?decomposition,Sensors?and?Actuators?B143,111(2009).
18.Y.Zeng,T.Zhang,M.Yuan,M.Kang,G.Lu,R.Wang,H.Fan,Y.He,H.Yang,Growth?and?selective?acetone?detection?based?on?ZnO?nanorod?arrays,Sensors?and?Actuators?B143,93(2009).
19.L.Wang,A.Teleki,S.E.Pratsinis,P.I.Gouma,Ferroelectric?WO
3nanoparticles?for?acetone?selective?detection,Chem.Mater.,20,237(2008).
20.M.Righettoni,A.Tricoli,S.E.Pratsinis,Si:WO
3?Sensors?for?highly?selective?detection?of?acetone?for?easy?diagnosis?of?diabetes?by?breath?analysis,Anal.Chem.,82,3581(2010).
Claims (according to the modification of the 19th of treaty)
1. the composition detecting for acetone, wherein said composition comprises:
(a) gamma-iron oxide (γ-Fe in the scope of 87.5wt% to 95.7wt%
2o
3),
(b) antimony (Sb) salt in the scope of 2.9wt% to 9.9wt%, and
(c) platinum (Pt) in the scope of 0.5wt% to 2.6wt%.
2. composition according to claim 1, wherein γ-Fe
2o
3by phonochemistry or arbitrarily other synthesis path prepare.
3. composition according to claim 1, wherein antimonic salt with oxide, carbonate, nitrate or arbitrarily the form of other salt add.
4. composition according to claim 1, wherein platinum with metallic forms, chloride, nitrate or arbitrarily the form of other salt add.
5. a method of preparing composition according to claim 1, wherein by the phonochemistry method comprising the following steps, prepare described composition:
(a) by adding water and hydrochloric acid, prepare Fe(NO3)39H2O (III) salt [Fe (NO
3)
39H
2o], aqueous solution separately of antimonic salt and platinum salt (being finally decomposed into metal platinum) and heat described solution at 100 ℃;
(b) with described aqueous solution that for example required ratio described herein will form in step (a) to form mixed solution;
(c) by the described mixed solution sonication forming in step (b) and add hydrazine to generate sediment during sonication;
(d) the described sediment forming in step (c) is centrifugal, wash and be dried to obtain gamma-iron oxide based composition and use thereof in packaging.
6. the method for the described composition of preparation according to claim 5, wherein antimonic salt with oxide, carbonate, nitrate or arbitrarily the form of other salt add.
7. the method for the described composition of preparation according to claim 5, wherein platinum with metallic forms, chloride, nitrate or arbitrarily the form of other salt add.
8. use composition according to claim 1 to manufacture a method for sensor, it comprises the following steps:
A) gamma-iron oxide based composition and use thereof in packaging is mixed to form slurry with isopropyl alcohol;
B) thus substrate is provided and it is heated gold electrode and platinum filament are attached to described substrate at the temperature of 1000 ℃;
C) provide described slurry prepared in step (a) and drip on the described substrate that is coated in rotation to manufacture the substrate that drips painting;
D) substrate of described painting is hardened at the temperature within the scope of 200 ℃ to 450 ℃;
E) cantar alloy heater coil is inserted into described dripping in the substrate being coated with; And,
F) by wire-bonded/soldering, the substrate that is coated with sensor is fixed on transistor outline (TO) type packaging body to form sensor.
9. method according to claim 8, wherein said sensor manufactures thick film on substrate or form and/or the block form of film.
10. method according to claim 8, wherein said substrate is selected from aluminium oxide or insulating material and is the form of pipe, planar structure or the microheater based on MEMS (micro electro mechanical system) (MEMS).
11. methods according to claim 8, wherein the described sensor of manufacturing detects the acetone concentration of 1ppm and sub-ppm under the existence of high-moisture amount.
12. compositions according to claim 1, wherein said composition is for the manufacture of sensor, and described sensor is for diagnosing diabetes and monitoring diabetic's abnormal acetone concentration.
Claims (14)
1. the composition detecting for acetone, wherein said composition comprises:
(a) gamma-iron oxide (γ-Fe
2o
3),
(b) antimony (Sb) salt, and
(c) platinum (Pt).
2. composition according to claim 1, wherein antimonic salt with oxide, carbonate, nitrate or arbitrarily the form of other salt add.
3. composition according to claim 1, wherein platinum with metallic forms, chloride, nitrate or arbitrarily the form of other salt add.
4. composition according to claim 1, wherein the concentration of gamma-iron oxide is in the scope of 87.5wt% to 95.7wt%.
5. composition according to claim 1, wherein the concentration of antimonic salt is in the scope of 2.9wt% to 9.9wt%.
6. composition according to claim 1, wherein the concentration of platinum is in the scope of 0.5wt% to 2.6wt%.
7. a method of preparing composition according to claim 1, wherein by the phonochemistry method comprising the following steps, prepare described composition:
(a) by adding water and hydrochloric acid, prepare Fe(NO3)39H2O (III) salt [Fe (NO
3)
39H
2o], aqueous solution separately of antimonic salt and platinum salt and heat described solution at 100 ℃;
(b) with described aqueous solution that for example required ratio described herein will form in step (a) to form mixed solution;
(c) by the described mixed solution sonication forming in step (b) and add hydrazine to generate sediment during sonication;
(d) the described sediment forming in step (c) is centrifugal, wash and be dried to obtain gamma-iron oxide based powders.
8. the method for the described composition of preparation according to claim 7, wherein antimonic salt with oxide, carbonate, nitrate or arbitrarily the form of other salt add.
9. the method for the described composition of preparation according to claim 7, wherein platinum with metallic forms, chloride, nitrate or arbitrarily the form of other salt add.
10. use composition according to claim 1 to manufacture a method for sensor, it comprises the following steps:
A) gamma-iron oxide based powders is mixed to form slurry with isopropyl alcohol;
B) thus substrate is provided and it is heated gold electrode and platinum filament are attached to described substrate at the temperature of 1000 ℃;
C) provide described slurry prepared in step (a) and drip on the described substrate that is coated in rotation to manufacture the substrate that drips painting;
D) substrate of described painting is hardened at the temperature within the scope of 200 ℃ to 450 ℃;
E) cantar alloy heater coil is inserted into described dripping in the substrate being coated with; And,
F) by wire-bonded/soldering, the substrate that is coated with sensor is fixed on transistor outline (TO) type packaging body to form sensor.
11. methods according to claim 10, wherein said sensor manufactures thick film or the form of film and/or the form of bulk on substrate.
12. methods according to claim 10, wherein said substrate is selected from aluminium oxide or insulating material and is the form of pipe, planar structure or the microheater based on MEMS (micro electro mechanical system) (MEMS).
13. compositions according to claim 1, are wherein used the described sensor of described composition under the existence of high-moisture amount, to detect the acetone concentration of 1ppm and sub-ppm.
14. compositions according to claim 1, the relevant disease that wherein said composition is used for diagnosing diabetes and has abnormal acetone concentration.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN1313/DEL/2012 | 2012-04-30 | ||
| IN1313DE2012 | 2012-04-30 | ||
| PCT/IN2013/000120 WO2013164836A1 (en) | 2012-04-30 | 2013-03-04 | A sensor composition for acetone detection in breath |
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|---|---|
| CN104040347A true CN104040347A (en) | 2014-09-10 |
| CN104040347B CN104040347B (en) | 2016-06-15 |
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| CN201380004960.9A Active CN104040347B (en) | 2012-04-30 | 2013-03-04 | For the sensor combinations thing that the acetone in breathing detects |
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|---|---|
| US (1) | US9470675B2 (en) |
| EP (1) | EP2845009B1 (en) |
| JP (1) | JP6175492B2 (en) |
| KR (1) | KR101974209B1 (en) |
| CN (1) | CN104040347B (en) |
| TW (1) | TWI596339B (en) |
| WO (1) | WO2013164836A1 (en) |
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| US9341632B1 (en) | 2014-07-23 | 2016-05-17 | Invoy Technologies, Inc. | Ketone measurement system capable of detecting correlations between measurements and user behaviors |
| US9459201B2 (en) | 2014-09-29 | 2016-10-04 | Zyomed Corp. | Systems and methods for noninvasive blood glucose and other analyte detection and measurement using collision computing |
| US10694978B2 (en) | 2015-05-14 | 2020-06-30 | Invoy Holdings, Llc | Breath analysis system, device and method employing nanoparticle-based sensor |
| US10379095B2 (en) * | 2015-11-25 | 2019-08-13 | Nitto Denko Corporation | Gas sensor element |
| US9554738B1 (en) | 2016-03-30 | 2017-01-31 | Zyomed Corp. | Spectroscopic tomography systems and methods for noninvasive detection and measurement of analytes using collision computing |
| CN108828017A (en) * | 2018-03-20 | 2018-11-16 | 武汉科技大学 | A kind of gas sensor and preparation method thereof towards acetone gas detection |
| PL232385B1 (en) | 2018-04-24 | 2019-06-28 | Akademia Gorniczo Hutnicza Im Stanislawa Staszica W Krakowie | Portable device intended for detection of biomarkers in exhaled air and method for detection of biomarkers in exhaled air |
| CN111874954B (en) * | 2020-07-22 | 2022-07-22 | 复旦大学 | Gas-sensitive nano material based on carbon particle modified mesoporous iron oxide nanorod structure, preparation process and application thereof |
| KR102337487B1 (en) * | 2020-10-07 | 2021-12-09 | 홍익대학교세종캠퍼스산학협력단 | Manufacturing Method For Exhalation Sensor To Detect Acetone Based On Zinc Oxide And Exhalation Sensor Manufactured Therefrom |
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| Publication number | Publication date |
|---|---|
| TWI596339B (en) | 2017-08-21 |
| KR101974209B1 (en) | 2019-04-30 |
| EP2845009A1 (en) | 2015-03-11 |
| EP2845009B1 (en) | 2017-07-19 |
| JP6175492B2 (en) | 2017-08-02 |
| WO2013164836A1 (en) | 2013-11-07 |
| WO2013164836A4 (en) | 2014-06-05 |
| TW201344190A (en) | 2013-11-01 |
| US9470675B2 (en) | 2016-10-18 |
| WO2013164836A9 (en) | 2014-05-01 |
| KR20150008044A (en) | 2015-01-21 |
| US20150301020A1 (en) | 2015-10-22 |
| CN104040347B (en) | 2016-06-15 |
| JP2015516071A (en) | 2015-06-04 |
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